KR20060006892A - Overbased amorphous alkaline earth metal salt in powder form and preparation method thereof - Google Patents

Abstract

A process for the preparation of overbased amorphous alkaline earth metal salts in powder form consisting essentially of isolated solid aggregated micelles of amorphous alkaline earth metal carboxylates of complexed fatty acids and complexed alkaline earth metal salts is described. The method for preparing the powder includes the step of precipitating and separating the solid particles from the liquid overbased alkaline earth metal composition.

Description

Powdered overbased amorphous alkaline earth metal salts and processes for making}

This application is a partial consecutive application of US Patent Application Serial No. 09 / 861,393, filed May 18, 2001. The entire contents of this patent application are incorporated herein by reference.

The present invention relates to overbased amorphous alkaline earth metal salts in powder form of fatty acids and methods for their preparation. Overbased powders are useful in many applications, including polymer stabilizers, lubricants, catalysts, oil well compositions, animal nutrition and cosmetics.

  The preparation of overbased calcium or barium salts of carboxylic acids, alkyl phenols and sulfonic acids is described in US Pat. 2,760,970; 2,760,970; 2,767,164; 2,798,852; 2,798,852; 2,802,816; 2,802,816; 3,027,325; 3,027,325; 3,031,284; 3,342,733; 3,533,975; 3,499,437; 3,773,664 and 3,779,922. The use of these overbased metal salts in halogen-containing organic polymers is described in US Pat. No. 4,159,973; 4,252,698 and 3,194,823. The use of overbased barium salts in stabilizer formulations has increased in recent years. This is mainly due to the fact that overbased barium salts have an advantageous performance over neutral barium salts. Advantageous performances associated with overbased barium salts include low plate-out, excellent color retention, good long term thermal safety performance, good miscibility with stabilizer components, and the like. Unfortunately, most of the overbased barium salts are dark in color, while these dark colored overbased barium salts are effective stabilizers for halogen-containing organic polymers, so their dark colors lead to fading of the final product. This feature essentially avoids the use of dark colored overbased barium salts in applications where light colored polymer products are desired.

In accordance with the teaching of US Pat. No. 4,665,117, photo-saturated alkali or alkaline earth metal salts are prepared in which alkyl phenols are used as promoters. However, alkyl phenols are also a major cause for the expression of the color of the final product. This problem is overcome by limiting the formation of colored species by using propylene oxide to replace the hydrogen of the phenolic hydroxyl group. However, due to the toxic nature of propylene oxide in principle, there are disadvantages associated with this approach. Propylene oxide is classified as a potential carcinogen and has been shown to be associated with cancer in laboratory animal inhalation studies. Propylene oxide is also listed as a powerful eye irritant, and prolonged exposure to propylene oxide vapor can cause permanent damage to the eye. In addition, propylene oxide is very flammable and explodes naturally under certain conditions. Propylene oxide boils at 94 ° F and flashes at -20 ° F. As a result, extreme care is required to handle propylene oxide at plant sites. Certain storage devices are required for propylene oxide and other safety features are also required. US Pat. No. 4,665,117 describes the use of propylene oxide at 150 ° C. At this temperature, propylene oxide will be in a gaseous state. Under these operating conditions, more than stoichiometric amounts of propylene oxide are required to fully carry out the reaction, since propylene oxide escapes from the reaction mixture, which requires further handling of excess propylene oxide.

As a method for removing heavy metals in the plastics industry, a liquid calcium-zinc stabilizer is required, but it is not practical as a substitute for barium-cadmium or barium-zinc. Low metal concentrations, poor miscibility, hazeiness in transparent products and plate out during processing in PVC severely limit the general tolerance of calcium-based liquid stabilizer compositions. Problems are also encountered in the stability of these compositions upon standing or storage. Storage stability is due to immiscibility in the metal salts used in the composition and is inhibited by increased turbidity, viscosity or insoluble solids over time. As a result, the liquid calcium composition is no longer homogeneous or easily poured and must be specially treated for use. U. S. Patent No. 5,322, 872 relates to stabilizing compositions of mixed metal carboxylades with improved storage stability. According to this patent, a complexing agent is added to the mixed metal carboxylate to improve storage stability. Complexing agents described in this patent include phosphines, phosphites, aromatic cyanide, aromatic hydroxy compounds, oximes and other compounds. U.S. Pat.Nos. 5,830,935 and 5,859,267 are also patented on methods of improving basic metal salts and methods of stabilizing halogen-containing polymers with such methods.

US Pat. Nos. 3,766,066 (hereinafter also referred to as '066) and 3,766,067 (hereinafter also referred to as' 067) are homogenized and carbonized with the aid of "conversion agents" such as water and alcohols. It describes the preparation of a solid calcium-containing micellar complex from calcium overbased organic acid salts. The '067 patent teaches that it is necessary to apply a salt solution in an inert organic liquid diluent to the homogenization step with vigorous stirring in the presence of water, alcohol or a mixture of alcohol and water to prepare the desired micelle complex from the overbased salt. Doing. Homogenization is achieved by producing crystalline particles characterized by a pattern corresponding to the x-ray diffraction pattern of the calcite by the phenomenon of "thickening" or "gelling". However, x-ray diffraction studies of the starting salt solution do not indicate the presence of any crystalline calcium carbonate. Indeed, the '066 patent teaches that calcium carbonate present in the starting non-homogenized solution does not appear amorphous. Amorphous metal salts or complexes present in the material are reliably transferred to the crystalline particles upon homogenization according to the '066 and' 067 patents. U. S. Patent 5,534, 169 also teaches the conversion of Newtonian overbased calcium carboxylates to non-Newtonian dispersion of calcite particles to produce materials useful for reducing friction. It is. U. S. Patent No. 5,830, 832 also describes the preparation of powdered calcium overbased soaps from branched oxo-acids.

Notwithstanding the art in the art as exemplified by the above patents, further improvements in the overbased alkaline earth metal salts of fatty acids, methods of preparing them and further improvements in their use in product application are required. have.

Summary of the Invention

The present invention relates to overbased amorphous alkaline earth metal salts in powder form of fatty acids. These particles include discrete solid aggregated particles of amorphous alkaline earth metal salts from the group consisting of carbonates, sulfates, sulfides and sulfites complexed with amorphous alkaline earth metal carboxylates of fatty acids. In a preferred form, the powders are alkaline earth metal carboxylates / carbonates. These powders are sometimes more simply referred to later as "overbased amorphous alkaline earth metal salt (s) in powder form" or "overbased amorphous alkaline earth metal carboxylate (s) / carbonate (s) in powder form". Overbased amorphous calcium and barium salts in powder form are preferably provided, and in a preferred form of the invention, the powders are essentially free of phenols or phenolic derivatives. Amorphous overbased salts in powder form are solid particles that are essentially aggregated micelles of amorphous metal salts such as metal carbonates complexed with amorphous metal carboxylates. Aggregated particles generally range in size from about 50 microns.

The invention also relates to a process for the preparation of overbased amorphous alkaline earth metal salts in powder form. The process involves reacting alkaline earth metal bases and fatty acids in the presence of a liquid hydrocarbon in a ratio of at least 1: 1 equivalent of metal base to fatty acids. Surfactants and catalysts are used to promote the reaction. The mixture is preferably acidified by carbonization to produce amorphous alkaline earth metal carbonates. In a preferred method, during carbonization, a dispersion of alkaline earth metal bases, liquid hydrocarbons, and aliphatic alcohols having 8 or more carbon atoms is added in relative amounts to produce a stable haze free liquid reaction product. Water is removed from the reaction product to obtain a shelf stable haze free liquid overbased alkaline earth metal salt. The overbased amorphous salt in powder form is then separated by adding a sufficient amount of solvent to the liquid hydrocarbon / alcohol of the haze-free liquid to allow particles of the overbased amorphous salt to aggregate and separate. Thereafter, the aggregated particles are separated by filtration and drying to a handleable state as a solid powder.

As reported in Applicant's prior US patent application Ser. No. 09 / 861,393, filed May 18, 2001, a stable amount was added by controlling the rate of dispersion of a relative amount of metal base, liquid hydrocarbon and aliphatic alcohol during carbonization. It has been found to be important to prepare a haze free liquid reaction product. There are many reasons believed to contribute to the formation of a stable haze-free liquid that is filterable to remove impurities and reaction byproducts. Until these findings are made in accordance with the principles of the present invention, for example, overbased calcium fatty acid salts that can be filtered at commercial or practical rates to remove unwanted impurities and reaction by-products to produce storage stable haze-free liquids. It is not considered possible to prepare them in actual or commercial processes. In contrast, it has been found that this result can be achieved by the continuous addition of dispersion or base slurry during carbonization. Metal base slurries are believed to prevent the formation of undesirable calcium carbonate crystals or byproducts in the desired overbased metal salt. These undesirable residues prevent the formation of a filterable, stable haze free product. In other words, the metal base slurry is added at a controlled rate that does not exceed the rate of the reaction to form the desired product. The reaction is controlled by the continuous or increased addition of metal bases, for example metal bases to produce readily available calcium ions for the desired reaction as opposed to allowing lime to react to form byproducts. Excess by-products or lime coated with calcium carbonate are believed to render the liquid product impossible to filter. When using this process, the desired product is produced by adjusting the pH during the reaction to neutralize the fatty acid and adding the base continuously to raise the pH to about 10-12 to produce dissolved metal ions that react with CO ₂ during carbonization. Manufacture. If the reaction rate is not controlled, the base does not dissolve, so it is believed that the solid base reacts or is coated with calcium carbonate to form undesirable byproducts. The formation of undesirable byproducts of the reaction makes the final product unstable and not filterable.

It has now been found that overbased amorphous salts in powder form can be prepared from haze free liquids of overbased alkaline earth metal fatty acid salts. These powders are suitable for use in many products including lubricants, catalysts, oil well compositions, animal nutrition and cosmetics. These are particularly useful for preparing mixed metal stabilizer compositions with zinc, cadmium or alkyltin carboxylates. Other metal compound stabilizers that are well known can be used when the metal component can also be barium, calcium, strontium, lead, bismuth or antimony, and mixtures thereof. Mixed metal stabilizer compositions provide thermal and / or light stability to vinyl halide resins such as polyvinyl chloride (PVC) and the like.

Many advantages are obtained by the products and methods in powder form of the invention. Powders provide storage stability overbased alkaline earth metal fatty acid salts. In particular, storage stability is achieved using powders free of phenols and phenolic derivatives such as phenolic reaction products. This is a particularly desirable advantage in terms of market efforts to reduce or eliminate these phenolic products due to environmental issues. In addition, as developed above, these phenols are chromophores. In addition, the improved storage stability for powders and mixed metal stabilizer compositions of the present invention has been demonstrated to surpass currently available products. In particular, presently useful liquid overbased calcium fatty acid carboxylates exhibit turbidity or haze progression, whereas the composition in powder form of the present invention remains stable over an extended period of time. The separated powders of the present invention also allow for easy handling and storage. The powders can be dispersed in liquid hydrocarbons and other solvents to form a haze free liquid. Thus, redispersion of the powder is not limited to a particular medium. The promoter and reaction diluent are removed from the powders. In addition, higher concentrations of calcium, for example up to about 25%, can be achieved upon redispersion. When mixed metal stabilizer systems containing overbased barium or calcium carboxylates in powder form are used in vinyl halide polymers, they have good horns with improvements in thermal stability, transparency and plate out resistance. Indicates Mars.

For example, in contrast to overbased crystalline powders in which crystalline needles or platelets negatively increase the viscosity or rheology of end-use products such as lubricants and emollients Overbased amorphous powders significantly improve the neutralization properties of acidic residues without negatively affecting the viscosity at end use. Improved detergency in end use is also achieved by the novel amorphous powders of the present invention. The above advantages, advantages and further understanding of the present invention will become apparent with reference to the following detailed description and preferred embodiments.

A. Haze of storage stability of overbased alkaline earth metal salts Overbased amorphous salt in powder form derived from free liquid

In one preferred form of the invention, the overbased amorphous salt in powder form is a storage stability of the amorphous overbased alkaline earth metal salts of fatty acids comprising alkaline earth metal carbonates, alkaline earth metal carboxylates of fatty acids, liquid hydrocarbons and aliphatic alcohols having 8 or more carbon atoms. Derived from a haze-free liquid, the liquid is preferably free of phenols or phenolic derivatives such as phenolic reaction products.

In another form of the invention, amorphous alkaline earth metal sulfates, sulfides or sulfites may be formed in place of carbonates, wherein the acid gases used in the process are sulfur dioxide, sulfur trioxide, carbon disulfide or hydrogen sulfide.

Overbased amorphous salts in powder form are precipitated from liquid overbased salts using a liquid precipitating agent or solvent, such as isopropyl alcohol, to liquid hydrocarbons and / or alcohols and glycols that may be present such that the solid particles of the overbased salts aggregate into amorphous particles. Separated by being formed by Aggregated particles of overbased salts are then obtained by filtration and drying. In order to eliminate the need to evaporate the volatiles, it is desirable to use a special apparatus for precipitating solids from the liquid salt or for granulating and collecting the powder, for example by spraying. Aggregated particle sizes for overbased amorphous salts range from about 50 microns, although particle size is not critical. These powders have been found to be dispersed in liquid hydrocarbons and other solvents to produce haze-free liquids with a wide range of end uses, as described later.

Liquid precipitants or other solvents such as methanol, ethanol, propanol, butanol and glycol ethers may be used to precipitate the powder or aggregated particles from the liquid overbased salts. Lower alcohols are preferred because they are more easily removed from the filtered product by drying. This solvent or liquid separates the crystalline lime particles as described in US Pat. Nos. 3,766,066 and 3,766,067, as described above in the background of the present invention, thereby converting the Newtonian overbased liquid into a non-Newtonian colloidal system. It has been used as a "conversion agent" for phone calls. In contrast, according to the invention, overbased amorphous salts are separated by adding an excess amount of solvent to the liquid hydrocarbon and alcohol phase of the haze-free overbased liquid. By so treating the haze-free overbased liquid of the present invention, the overbased amorphous salt in powder form can be separated in contrast to the crystalline lime-containing powder of the preceding patents mentioned. Thus, when a solvent is added in a sufficient amount of about 5 with respect to the haze-free overbased liquid 1, the overbased amorphous salt aggregates to produce the overbased amorphous product in powder form of the present invention. The method is believed to be solvent extraction of liquid hydrocarbons from liquid overbased compositions.

Perchloric, generally C ₁₂ containing the ready-made liquid fatty acids of the carboxylate is, for example, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid (behenic acid) in the saturated fatty acid - C ₂₂ fatty acid. Unsaturated fatty acids include palmitoleic acid, oleic acid, linoleic acid and linolenic acid. Among these fatty acids, oleic acid is presently preferred for producing overbased liquid carboxylates.

The alkaline earth metal of the salts described above is selected from the group consisting of calcium, barium, magnesium and strontium. For example, overbased calcium oleate in powder form has been prepared. These overbased calcium salts in powder form contain amorphous calcium carbonate complexed with calcium oleate.

Aliphatic alcohols having at least about 8 carbon atoms, more preferably carbon atoms, such as isodecanol, dodecanol, octanol, tridecanol and tetradecanol, in the preparation of liquid overbased salts in which amorphous salts in powder form are derived It is important to have 8-14 alcohols. Isodecanol is presently preferred. It has been found that when higher aliphatic alcohols are used in preparing liquid overbased products, phenol can be excluded from the reactants as promoter. This is a particularly advantageous feature of the present invention when it is undesirable to have the phenol or phenolic reaction product included in the preparation or use of overbased amorphous salts in powder form.

Although not strictly bound by theory, it is believed that the liquid overbased alkaline earth metal salts of fatty acids are thermodynamically stable microemulsions. Microemulsions have micelles and continuous phases. The micelles consist of amorphous alkaline earth metal carbonates and amorphous alkaline earth metal carboxylates of fatty acids. The continuous phase of the microemulsion consists of liquid hydrocarbons and aliphatic alcohols or glycols that may be present. The present invention relates to the separation of particles that are aggregated micelles of amorphous salts to form overbased salts in powder form.

The overbased amorphous metal salt in powder form is prepared to contain at least 8% to about 70% by weight alkaline earth metal. In the case of overbased calcium salts, up to about 8% by weight of calcium can be produced, and in the case of barium salts up to about 30% by weight of barium can be produced. For example, it has been found suitable to use glycols or glycol ethers with higher aliphatic alcohols in the preparation of better overbased products containing about 15 to 70% by weight of metal. Glycols or glycol ethers are selected from the group consisting of diethylene glycol monobutyl ether [butyl carbitol ^® , triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof Can be selected.

B. Overbased  Basic methods and main features for preparing liquids and powders derived therefrom

Storage Stability of Overbased Alkaline Earth Metal Salts of Fatty Acids The process of the present invention for preparing haze-free liquids employs alkaline earth metal bases with an equivalent ratio of metal base to fatty acids greater than 1: 1 in the presence of a mixture of liquid hydrocarbons. Reacting fatty acids. Surfactants and catalysts promote the reaction. The mixture is acidified and preferably carbonized to produce amorphous alkaline earth metal carbonates. During carbonization, dispersions containing alkaline earth metal bases, liquid hydrocarbons, and aliphatic alcohols having 8 or more carbon atoms are added in relative amounts while controlling the rate of base addition to produce a stable haze-free liquid reaction product. Water is removed from the reaction product to produce a storage stable haze free liquid overbased alkaline earth metal salt. In general, it is preferable to carry out the whole process in the absence of free oxygen, and a nitrogen atmosphere is used for this purpose.

As developed above, one of the important features of the process is the step of adding a dispersion of alkaline earth metal bases, liquid hydrocarbons and aliphatic alcohols having 8 or more carbon atoms while controlling the base addition rate during carbonization to produce a stable haze-free liquid. The addition of base dispersions in liquid hydrocarbons and aliphatic alcohols has been found to protect or passivate the base to form a stable haze-free liquid reaction product. By protecting or surface stabilizing the base, carbonization proceeds to produce amorphous alkaline earth metal carbonates. Unexpectedly, the reaction proceeds without the need to remove water during the reaction, producing a very stable haze-free liquid reaction product. At the end of the reaction, water is removed to a level of less than 1%, more preferably less than 0.3% or less than 0.1% upon obtaining a storage stable liquid overbased salt. Removal of water added or formed by the reaction during the reaction is essential because the water forms a separate phase that delays the formation of the reaction product or storage stable haze-free liquid.

Another feature of the process includes filtering the reaction product at a product filtration rate of at least about 300 ml per 10 minutes to produce a storage stable or thermodynamically stable liquid. In a preferred form of the invention, the product produced is filterable to remove unwanted byproducts and to improve the storage stability of the overbased liquid. For example, a Buchner with a diameter of 15 cm using a Whatman No. 1 filter and a diatomaceous earth filter aid (Celite ^® 512-577) under a vacuum of about 25 to 30 inches of Hg. When using a funnel, the product can be filtered at a satisfactory rate. One of the important findings of the process of the present invention is the ability to filter the reaction product to form a stable haze free liquid at a filtration rate that could not be achieved previously. This was especially the case where a higher level of metal content in the overbased liquid was required, in particular an overbased calcium liquid. Thus, filtration removes undesirable impurities including silica, iron oxide and other metal species, unreacted calcium hydroxide, calcium carbonate and other oxides that may contribute to the lack of stability. These byproducts or impurities may constitute up to about 6% of the reaction byproducts.

Throughout this specification and claims, the term “basic” or “overbased” as applied to alkaline earth metal salts is used to refer to a metal composition that is greater than the stoichiometric ratio of the total metal to fatty acid residues of the non-neutral metal salt. do. That is, the equivalent number of metals is greater than the equivalent number of fatty acids. In some instances, the extent to which excess metal is found in basic metal salts is described in terms of “metal ratio”. As used herein, the metal ratio refers to the ratio of total alkaline earth metals in the fat soluble composition to the equivalent number of fatty acids or organic residues. Basic metal salts have often been referred to in the art as "overbased" or "superbased" to indicate the presence of excess basic components.

The process of the present invention can be used to prepare storage stable liquids and separated powders of amorphous alkaline earth metal carboxylates of fatty acids. As described above, the process can be carried out without the use of phenolic accelerators or phenolic reaction products. Thus, overbased barium fatty acid carboxylates in liquid and powder form can be prepared without the need for phenol or phenolic reaction products to achieve storage stability haze-free liquids. In the case of overbased calcium fatty acid carboxylates in liquid and powder form, storage stability products are obtained without phenols when using aliphatic alcohols having 8 or more carbon atoms.

Alkaline earth metal bases used as reaction components may originate from any alkaline earth metal, of which calcium and barium bases are particularly preferred. Metal bases include metal oxides and metal hydroxides, and in some examples include metal sulfides, metal hydro sulfides, and the like. Phenol-based components or reactants may preferably be excluded from the reaction in the case of liquid overbased calcium products, while phenol or alkyl phenols may be included to obtain a liquid overbased product. As described above, as identified above, fatty acids or mixtures thereof can be used in the reaction mixture. For example, the surfactant that catalyzes the reaction is alkaline earth metal carboxylates of fatty acids formed in the reaction system. General purpose interfaces identified under the trade name Tween, which is a polyoxyethylene derivative of fatty acid partial esters of fatty acid partial esters of sorbitol anhydride, in particular ethoxylated sorbitol, and polyisobutylene succinic acid It may include an active agent. It is also desirable to include catalysts for promoting the rate of the reaction, such as propionic acid, citric acid, acetic acid and adipic acid. Hydrocarbon liquids and liquid reaction products used in the process generally include all hydrocarbon diluents. Most commonly, liquid hydrocarbons are selected from the group of oils, mineral spirits and non-aromatic hydrocarbons.

C. Amount of Reactant and Catalyst

The amount of alkaline earth metal base used in the preparation of the basic salt is an amount of at least 1 equivalent of base per equivalent of fatty acid or organic residue, and more generally will be an amount sufficient to provide at least 3 equivalents of metal base per acid equivalent. Higher amounts may be used to form more basic compounds, and the amount of metal base included may be a certain amount up to an amount that is no longer effective to increase the proportion of metal in the product. When preparing the mixture, the amount of fatty acids and alcohols included in the mixture is not critical except that the ratio of the metal base equivalents in the combination of the other components in the mixture must be greater than 1: 1 to give a basic product. More generally, this equivalent ratio will be at least 3: 1. If phenol can be present in the preparation of overbased calcium, the equivalent ratio of monocarboxylic acid to phenol can be at least about 1.1: 1; That is, the monocarboxylic acid is present in excess of phenol.

The range of hydrocarbon oils, aliphatic alcohols (preferably isodecanol), butyl carbitol and triethylene glycols can be determined by the mixture of metal carbonates in the presence of alkaline earth metal fatty acid salts (i.e. Ca oleate) serving as the main surfactant. Water and surfactant (inner phase) and surfactants, cosurfactants, and hydrocarbons (outer continuous phase) are selected to form stable inverse microemulsions.

The acceptable ratio of hydrocarbon oil to cosurfactant aliphatic alcohol (isodecanol) is from about 2: 1 to about 4: 1, with about 2: 1 being preferred. Glycol ethers can be used in about 1-15% of the final product, butyl carbitol preferably in about 6%, and triethylene glycol in about 0-2%, preferably about 0.6%. .

The lime slurry added to oleic acid in the reaction is easily pumpable with a general composition of about 40-50% lime, about 25-40% hydrocarbon oil, about 10-25% isodecanol and about 0-10% butyl carbitol Formulated in a mixture. The amount of butyl carbitol required to make the pumpable slurry increases with increasing percentage of lime in the slurry.

The reaction mixture for superbasic calcium oleate after addition of slurry and carbonization with carbon dioxide preferably has the following composition range:

Ca oleate (surfactant) about 15-30%

Ca carbonate about 9-35%

About 30 to 35% of hydrocarbon oil

Isodecanol (adjuvant surfactant) about 15-18%

Butyl carbitol about 4-6%

Triethylene glycol about 0-0.8%

The catalyst, propionic acid or lower aliphatic mono, di or tricarboxylic acid is used in an amount of about 0 to 0.1% of the final reaction mixture.

Substitution of magnesium, strontium or barium for calcium in overbased salts is made on the basis of the equivalents of the metal oxides. Based on the final reaction mixture, the following amounts can be used:

Ca (OH) ₂ (lime) about 15-30%

Mg (OH) ₂ about 12-24%

Sr (OH) ₂ about 25-50%

Ba (OH) ₂ about 35-50%

The carbonization step involves treating the mixture described above with an acidic gas in the absence of free oxygen until a titratable basicity is determined using phenolphthalein. In general, titratable basicities reduce the number of bases to about 10 or less. The mixing and carbonization steps of the present invention preferably require general process conditions besides the exclusion of free oxygen. The base, fatty acid and liquid hydrocarbon can be mixed and generally heated and then treated with carbon dioxide as an acidic gas and the mixture heated to a temperature sufficient to remove some of the water contained in the mixture. Treatment of the mixture with carbon dioxide is preferably carried out at elevated temperatures, and the temperature range used in this step can be any temperature above ambient temperature up to about 200 ° C, more preferably between about 75 ° C and about 200 ° C. May be temperature. Higher temperatures may be used, such as 250 ° C., but there are no obvious advantages in using these higher temperatures. Typically a temperature of about 80 ° C. to 150 ° C. is satisfactory.

As used herein and in the claims, the term “acidic gas” means a gas that will produce acid upon reaction with water. That is, such gases such as sulfur dioxide, sulfur trioxide, carbon dioxide, carbon disulfide, hydrogen sulfide and the like are examples of acidic gases useful in the process of the present invention. Among these acids, sulfur dioxide and carbon dioxide are preferred, and carbon dioxide is most preferred. When carbon dioxide is used alkaline earth metal carbonates are formed. If sulfur gas is used, sulfates, sulfides and sulfites are formed.

D. Halogen-containing Polymer

Halogen-containing polymers such as vinyl halide resins most commonly stabilized with the basic metal salts of the present invention are polyvinyl chlorides. However, it should be understood that the present invention is not limited to specific vinyl halide resins or copolymers thereof such as polyvinyl chloride. Other halogen-containing resins used in the present invention and listing the principles of the present invention include chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated polyvinyl chloride and other vinyl halide resin types. As understood herein and familiar with the art, vinyl halide resins are generic terms and are used with these comonomers or with other comonomers such as ethylene, propylene, vinyl acetate, vinyl ether, vinylidene chloride, methacrylate, acrylate, styrene, and the like. It is employed to define polymers or resins which are generally derived by polymerization or copolymerization of vinyl monomers in the absence of vinyl chloride. The simple case is the conversion of vinyl chloride H ₂ C═CHCl to polyvinyl chloride (CH ₂ CHCl—) _n , where the halogen is bonded to a carbon atom of the polymer carbon chain. Other examples of such vinyl halide resins include vinylidene chloride polymers, vinyl chloride-vinyl ester copolymers, vinyl chloride-vinyl ether copolymers, vinyl chloride-vinylidene copolymers, vinyl chloride-propylene copolymers, chlorinated polyethylene, and the like. do. Although other such as bromide and fluoride can be used, of course, the vinyl halide commonly used in industry is chloride. Examples of the latter polymers include polyvinyl bromide, polyvinyl fluoride and copolymers thereof.

Metal compound heat stabilizers of vinyl halide resin compositions are well known. Such metal compounds are provided to capture publicly released HCl that thermally processes the vinyl halide resin composition into its final form. The metal can be, for example, lead, cadmium, barium, calcium, zinc, strontium, bismuth, tin or antimony. Stabilizers are generally metal salts of carboxylic acids, advantageously metal salts of C ₈ -C ₂₄ carbon chain linked monocarboxylic acids such as laurate, oleate, stearate, octoate or similar fatty acid salts. Metal salts of alkyl phenates can be used. Mixed metal salts such as acids and methods for their preparation are familiar to those skilled in the art. Mixed metallic carboxylates comprising calcium / zinc or barium / zinc blends alone and calcium / zinc or barium / zinc blends mixed with other stabilizers or additives such as beta-diketones, phosphite salts and phenolic antioxidants It is used. Metal stabilizers are mixed metal salts of carboxylic acids. Mixed metal salts of these acids and methods for their preparation are familiar to those skilled in the art.

E. Final Concentration for Product in Liquid or Powder Form

As described above, the product in liquid or powder form of the present invention can be used in many end products such as lubricants, catalysts, oil well compositions, animal nutrition and cosmetics. Other specific examples include wallpaper, flooring (vinyl tiles and inlays), medical equipment, dip coating, chair mats, banner films, pigment dispersions, vinyl siding, piping ( piping, fuel additives, cosmetics, ceiling tiles, roofing films, wear layers, game balls or toys, teeters, fencing, corrugated wall panels, dashboards and mobile boot (shifter boot).

For example, the overbased amorphous metal carboxylates in liquid and powder form of the following examples can be used in the following applications.

1. Products in liquid and powder form can be used in PVC stabilizer components with high metal concentrations. The material in powder form can be used as in the stabilizer in powder form or readily dispersed in the light flux to produce a concentrated stabilizer component having only mineral oil as diluent.

2. The product in dispersed powder form can be used as a nanoparticle template to create a microporous substrate having defined size pores of about 0.1 μm in diameter. Other nanoparticle applications may include reinforcing or non-reinforcing films for plastics, and radiopaque or visually transparent fillers (Ba) for pharmaceutical applications.

3. Products in powder form, dispersed into oils and fuels, can be used in lubricating oils as detergents and acid neutralizers.

4. An overbased amorphous calcium oleate powder prepared in a nontoxic formulation can be used as a fat mimetic. The material has an amorphous metal core (calcium carbonate) with a fatty acid coating.

5. The overbased calcium oleate / carbonate in powder form can be used as a high calcium component dietary supplement for animal or human nutrition. Small particle size, and particulate fatty acid salt coating make the material more tasty and functional than uncoated calcium carbonate. The substance may also be provided to neutralize excess gastric acid.

6. The small size, fatty acid coatings and solid properties of the particles make them suitable as ingredients in skin care products as emollients and acid neutralizers.

7. Liquids and powders, dispersed in suitable carriers, may be used in metalworking lubricant formulations.

8. Products in liquid and powder form may be used as lubricating additives in oil well drilling applications in drilling mud formulations.

9. Products in liquid and powder form may be used in oil recovery fluids, floating fluids, spotting fluids, fluid loss components of drilling muds, and cementing fluids in oil well operations.

10. When combined with a cationic water soluble polymer (hydrogel), the powder can be used as an oil spill absorber, an oil absorbing component of an air filter, to improve indoor air quality.

11. The powder can be used as a component of the coating formulation to improve the water-repellency and anti-corrosion quality of the film.

The following examples illustrate the preparation of haze-free liquid overbased salts according to the process of the invention (Examples 1 to 6 and 10) and the overbased amorphous metal salts in powder form derived therefrom (Examples 7 to 9, 11 and 12). Indicates. These examples are not to be considered as limiting the scope of the invention. Unless indicated otherwise in the following examples, and also in the specification and claims, all parts and percentages are by weight and all temperatures are in Fahrenheit (° F).

Example 1

10% Overbased Calcium Oleate / Carbonade

Phenol-free 10% overbased calcium oleate / carbonate was prepared according to this example. A mixture of 308.42 g (1.100 moles) of oleic acid, 213.15 g of mineral oil, 154.14 g of isodecyl alcohol, 63.08 g of butyl carbitol, 8.70 g of triethylene glycol, 26.97 g of water and 0.87 g of propionic acid was heated to 190 ° F. with stirring under a nitrogen atmosphere. . To the stirred mixture, a dispersion comprising 38.98 g of mineral oil, 13.86 g of isodecyl alcohol, 3.71 g of butyl carbitol and 43.28 g (0.5498 mol) of lime was continuously added for about 33 minutes to prepare a calcium oleate solution in the mixture. The dispersion was added at a rate of about 3 g per minute. At this point in the reaction, the mixture was tested for basicity with phenolphthalein (pH about 10-12). Thereafter, the mixture was continuously added with a dispersion containing 276.25 g of mineral oil, 98.23 g of isodecyl alcohol, 26.31 g of butyl carbitol and 306.75 g of lime (3.897 mol) over a period of about 3 hours 56 minutes. Was treated with carbon dioxide at 195 to 200 ° F. at 1.5 SCFH. The dispersion was also added at a rate of about 3 g per minute. The basicity of the reaction was checked to maintain basicity during the reaction. If the reaction mixture was tested almost neutral to phenolphthalein, carbon dioxide addition was stopped. Thereafter, the reaction mixture was heated to 300 ° F. and a total of 99.36 g of water was removed via a Dean-Stark trap. The resulting product mixture was stirred and 24.00 g of filter aid (diatomaceous earth) were added. The product mixture is suction filtered at about 300 ml per 10 minutes as described above in the specification to give a clear, yellowish brown, movable liquid filtrate of overbased calcium oleate / carbonate that remains transparent upon cooling to room temperature. The filtrate was analyzed to contain 10.4 weight percent calcium.

Example 2

14% overbased calcium oleate / carbonate

Phenol-free overbased calcium oleate / carbonate containing 14% by weight of calcium was prepared according to this example. 9.89% of overbased calcium oleate / carboxylate prepared by the method of the previous example in a resin kettle with 3 liters equipped with an overhead stirrer, two gas input tubes, a thermocouple, a heating mantle and a Dean-Stark trap with a condenser 1700 g and 42.5 g deionized water were added. The mixture was heated to 195 ° F. with stirring under a nitrogen atmosphere and a slurry containing 385 g of hydrated lime (94% calcium hydroxide), 231 g of hydrocarbon oil, 96.25 g of isodecyl alcohol and 57.75 g of butyl carbitol was added at a rate of 3.42 g per minute. Applied over a period of 45 minutes. Five minutes after slurry addition, carbon dioxide was added to the reaction at a rate of 1.2 standard cubic feet per hour. During carbonization, the temperature was maintained at 195-200 ° F. and the pH was monitored as in Example 1.

After completion of the slurry addition, carbon dioxide addition was continued until the reaction mixture became neutral as indicated by the colorless sample when tested with phenolphthalein. The reaction mixture was then heated to 300 ° F., water was added and water produced during the reaction was removed via a Dean-Stark trap. 75 g of diatomaceous earth was added to the dehydrated reaction product and the product was suction filtered as described above in Example 1 to obtain a clear, tan, movable liquid filtrate of overbased calcium oleate / carboxylate, which was clear upon cooling at room temperature. Remained. The filtrate was analyzed and found to contain 14.5% by weight of calcium.

Example 3

10% Overbased Calcium Oleate / carbonate, GRAS Indirect Food Additive Formulation

A phenol-free 10% overbased calcium oleate / carbonate containing only materials generally recognized as stable as indirect food additives was prepared as follows. A mixture of 520.6 g (1.85 moles) of oleic acid, 522 g of Shellflex ^™ 6111 light mineral oil, 259 g of dodecyl alcohol and 32.4 g of propylene glycol was heated to 180 ° F. and 2.0 g propionic acid and 15.0 g water were added. To the stirred reaction mixture was added a slurry comprising 345.6 g of Shellplex 6111, 172.8 g of dodecyl alcohol, 21.6 g of propylene glycol and 540 g of lime (94% available as calcium hydroxide) at a rate of 4.0 g per minute. Approximately 41 minutes after the slurry was added, the oleic acid was neutralized and excess lime was present and partially dissolved to yield an apparent pH of 11.4. Thereafter, carbon dioxide gas was passed through the surface addition tube through the surface addition tube at a rate of approximately 495 ml / min to obtain a pH of 10.5 to 11 during slurry addition (approximately 5.25 hours) while slightly cooling the reaction temperature while maintaining it at 190 to Kept at 192 ° F. Once approximately 1080 g of slurry was added, the slurry addition was stopped and carbon dioxide addition continued until the pH of the reaction dropped to 7.5 (approximately 7 minutes). The reaction was carefully placed under 22.5 inches of vacuum and heated to 310 ° F. for 1.75 hours to remove added water and reactant water through a Dean-Stark tube. The reaction was kept at 310 ° F. and 30 g of diatomaceous earth filter aid was added. The product was heated and filtered by suction as described in the previous example at a rate of 545 ml / 10 min to obtain a clear tan movable filtrate of overbased calcium oleate / carbonate, which remained transparent upon cooling to room temperature. It was. The filtrate was analyzed and found to contain 10.5% by weight of calcium. The infrared spectrum of the material peaked at 864 cm ⁻¹ , which is characteristic of amorphous calcium carbonate. The physical state of calcium carbonate in the material prepared in this example was analyzed by X-ray powder pattern and infrared spectrum for crystallinity. Amorphous calcium carbonate has infrared absorption at 864 cm ^-1 according to Anderson's paper "Infrared Spectra of Amorphous and Crystalline Calcium Carbonate" and Brecevic, Acta Chemical Scandinavica 45 (1991) 1018-1024. Other crystalline polymorphic calcium carbonates, calsites, aragonites and batelites have corresponding infrared absorption at 877, 856 and 877 cm ⁻¹ , respectively.

Example 4

15% overbased calcium oleate / carbonate

Highly overbased calcium oleate / carbonate containing 15.4% by weight of calcium was prepared by the following process. To a mixture of 1700 g of 11.4% overbased calcium oleate / carbonate liquid prepared according to the previous example 50 g of water was added and the mixture was heated to 190 ° F. under stirring at 1000 rpm. In the mixture, 500 g of lime (94% useful as calcium hydroxide), 320 g of Shellflex 6111 light mineral oil, 160 g of dodecyl alcohol and 20 g of propylene glycol were charged over a period of 3 hours 40 minutes at a rate of 3.97 g per minute at a rate of 3.97 g per minute. Was added. Two minutes after the slurry was added, carbon dioxide gas was introduced into the reaction mixture through a subsurface addition tube at a rate (approximately 450-550 ml / min) to produce and maintain a value of 10.5-11. After the time required to add the required amount of lime slurry, the slurry addition was stopped and carbon dioxide addition continued until the pH of the reactant dropped to 7.5 (about 10 minutes). The reaction was then heated while slowly heating to 310 ° F. under a vacuum of 22.5 ″. The water and reactant water were removed via a Dean-Stark trap. The reaction mixture was then bed of diatomaceous earth (filtration aid). Filtration through gave a clear, tan, movable filtrate of highly overbased calcium oleate / carbonate, analyzed by material containing 15.4% by weight of calcium, infrared spectrum of material at 864 cm ^-1 , amorphous carbonic acid Characteristic peaks for calcium are shown.

Example 5

14% overbased strontium oleate / carbonate

Phenol-free strontium oleate / carbonate containing about 14% strontium was prepared by the following process. 413 g of oleic acid, 600 g of ShellFlex 6111 light mineral oil, 300 g of isodecyl alcohol, 40 g of butyl carbitol and 4 g of triethylene glycol were heated to 176 ° F. and 1000 g of strontium hydroxide octahydrate was added. 550 g of water was removed via a Dean-Stark trap with the aid of a nitrogen sparge at 2.0 SCFH while the reaction mixture was heated to 275 ° F. over a 2.5 hour period. After the water removal rate was slowed down, nitrogen sparging was stopped and carbon dioxide gas was added to the reaction at a rate of 450 ml / min via the subsurface addition tube, and the water formed was continuously removed. Seven hours after addition of carbon dioxide at 250-275 ° F., the carbon dioxide was stopped, the temperature of the reaction was raised to 300 ° F. and the remaining water was removed under the assistance of nitrogen sparging at 2.0 SCFH. The reaction was then filtered hot by suction with the aid of a filter aid to yield an overbased strontium oleate carbonate as a pale yellow transparent movable liquid. The product was analyzed and found to contain 14.25% by weight of strontium.

Example 6

4.5% overbased magnesium oleate / carbonate

Phenol-free magnesium oleate / carbonate containing about 4.5% magnesium was prepared by the following process. A mixture of 529.3 g of oleic acid, 600 g of ShellFlex 6111 light mineral oil, 400 g of isopropyl alcohol, 350 g of isodecyl alcohol and 400 g of water was heated to 140 ° F. and 400 g of magnesium hydroxide were added. Neutralizing the acid with magnesium hydroxide raises the temperature to 167 ° F. Carbon dioxide gas was passed into the reaction mixture through a subsurface addition tube at a rate of 225 ml / min for 6 hours during which the temperature was gradually raised to 223 ° F. and 720 ml of a mixture of water and isopropyl alcohol were removed. The temperature was raised to 305 ° F. and the remaining water was removed with the aid of carbon dioxide addition. The carbon dioxide addition was stopped and the hot reaction mixture was suction filtered with the aid of a filter aid to give the overbased magnesium product as a clear pale yellow movable liquid. The product was analyzed and found to contain 4.5 wt% magnesium.

Example 7

21.38% Overbasic Amorphous Calcium Oleate / Carbonate Powder

To 1000 g of rapidly stirred isopropyl alcohol was added 200 g of overbased calcium oleate / carbonate containing 10.5 wt% calcium (product from Example 3) in a stable stream over 5 minutes. The mixture was stirred at rt for 1 h and then suction filtered. The filter cake was washed with 2 × 100 g of isopropyl alcohol, inhaled until possible to dry and allowed to dry overnight at room temperature. The powder obtained did not exhibit crystalline properties by the x-ray powder pattern and was easily dispersed in mineral oil to obtain a transparent, isotropic, non-viscous dispersion. The powder was found to contain 21.38 weight percent calcium. The infrared spectrum of the powder [nujol mull] showed a peak at 866 cm ⁻¹ , which is characteristic of amorphous calcium carbonate.

Example 8

20.2% Overbased Amorphous Calcium Oleate / carbonate Powder

Overbased amorphous calcium oleate / carbonate in powder form was prepared according to the following examples. 500 g of rapidly stirred and heated refluxed isopropyl alcohol, 500 g of overbased calcium oleate / carbonate (product of Example 1 above) containing 9.75% by weight of calcium was added over a period of 15 minutes. The mixture was allowed to reflux for a further 1/2 hour before cooling to 90 ° F. and suction filtration. The collected solid was washed with 2 × 125 g of isopropyl alcohol and aspirated to dry as much as possible. The solid product was allowed to dry overnight at room temperature to yield 262 g of an off-white solid, which was analyzed and contained 20.2% by weight of calcium. The material was readily dispersed in 70% solids at the light flux to give a clear, movable dispersion having a calcium content of 13.83% by weight. The infrared spectrum of the powder (nusol water) showed a peak at 866 cm ^-1 , which is characteristic of amorphous calcium carbonate. The powder particles dispersed in the alcohol exhibited an average particle diameter of 0.112 microns.

Example 9

28% Overbasic Amorphous Calcium Oleate / Carbonate Powder

Overbased amorphous calcium oleate / carbonate powder in powder form was prepared according to the following examples. 200 g of overbased calcium oleate / carbonate liquid dispersion (prepared by Example 4 above) containing 15.4% by weight of calcium was added to 1000 g of rapidly stirred isopropyl alcohol in a stable stream for a period of 5 minutes. The mixture was stirred for an additional hour at room temperature, then suction filtered, washed with 2x100 ml of isopropyl alcohol and aspirated to dryness as far as possible. The product was allowed to dry overnight at room temperature in air to give a free-flowing off-white solid, which was analyzed to contain 28 wt% calcium. The infrared spectrum of the powder (nusol water) showed a peak at 866 cm ^-1 , which is characteristic of amorphous calcium carbonate. The X-ray powder pattern only showed a wide range of peaks and no peaks from calcite (crystalline calcium carbonate). The powder dispersed in the alcohol had an average particle diameter of 0.0566 microns.

Example 10

30% overbased amorphous barium oleate / carbonate

Phenol-free overbased amorphous barium oleate / carbonate was prepared according to the following examples. 502.5 g of oleic acid, 581 g of HVI mineral oil, 200.0 g of Epal ^TM 14-18 (mixture of aliphatic alcohols having 14 to 18 carbon atoms), 102 g of butyl carbitol (diethylene glycol monobutylether) and 10.2 g of triethylene glycol Was heated to 178 ° F. under a slow nitrogen stream. To the heater reaction mixture was added 1034.1 g of barium hydroxide monohydrate in three increments over a 45 minute period. The temperature of the reaction mixture was then raised to 280 ° F. over a period of 1 hour and 75.6 g of water were removed via the Dean-Stark trap with the aid of a nitrogen flow of 2 SCFH. Reduce the nitrogen flow to 1 SCFH and add carbon dioxide over a 5 1/2 hour period through the subsurface addition tube at a rate of about 300 ml / min, during which the temperature is gradually raised from 280 ° F to 300 ° F and dewatered. Removed after 2 hours at a rate of approximately 7.5 g every 15 minutes via a stock trap.

At the end of the carbon dioxide addition time, the reaction was carefully placed under 22 inches of vacuum and the remaining water was removed with a small amount of butyl carbitol. The total water removed was 210 g. After 30 minutes, the vacuum was released and 40 g of filter aid (diatomaceous earth) were added. The inorganics were suction filtered to give a clear, tan movable liquid which was analyzed to contain 29.7% by weight of barium.

Example 11

45.2% Overbasic Amorphous Barium Oleate / carbonate Powder

Phenol-free overbased barium oleate / carbonate containing 29.7% by weight of barium (prepared by Example 10) was poured into 1000 g of isopropyl alcohol with rapid stirring in a slow stream in 5 minutes. The mixture was stirred at rt for 1 h, then filtered by suction, washed with 2 × 100 g of isopropyl alcohol and aspirated to dry as much as possible and then dried in air overnight. The product, off-white powder, contained 45.2% by weight of barium in the analysis.

Example 12

45.5% Overbasic Amorphous Barium Oleate / Phenate / carbonate Powder

A phenol-containing overbased amorphous barium oleate / phenate / carbonate liquid containing 45.5% barium was prepared according to Example 10 with the addition of phenol to the reaction mixture as described, for example, in US Pat. No. 5,830,935. It was. 200 g of the overbased barium oleate / phenate / carbonate was added to 1000 g of rapidly stirred isopropyl alcohol at room temperature over a period of 5 minutes. The mixture was stirred for 1 1/2 hours followed by suction filtration, 2x100 g of isopropyl alcohol was washed, sucked to dry as much as possible and allowed to dry in air. The product, pink powder, was analyzed and found to contain 45.5% by weight of barium.

The foregoing description is provided to describe certain aspects of the present invention and is not intended to limit the present invention thereby. As such, the present invention is not limited to the above-described embodiments, but rather, those skilled in the art will appreciate that alternative embodiments will be understood in terms of the above-described technology falling within the scope of the present invention.

Claims (46)

Powdered salts of fatty acids consisting essentially of discrete solid aggregated micelles of amorphous alkaline earth metal carboxylates of fatty acids and complexed salts of amorphous alkaline earth metal salts from the group consisting of complexed carbonates, sulfates, sulfides and sulfites Ready-made amorphous alkaline earth metal salts. The salt in powder form of claim 1, wherein the micelle is an aggregate of complexed salts having a particle size on the order of about 50 microns. The salt in powder form according to claim 1, wherein the fatty acid is a C ₁₂ -C ₂₂ fatty acid. The salt in powder form according to claim 1, wherein the fatty acid is oleic acid. The salt of claim 1, wherein the alkaline earth metal is selected from the group consisting of calcium, barium, magnesium and strontium. The salt in powder form according to claim 1, wherein the alkaline earth metal is calcium. 2. The salt of claim 1 wherein the overbased alkaline earth metal salt is calcium oleate / carbonate. The salt of claim 1, wherein the salt is in powder form to disperse in liquid hydrocarbon to form a haze free liquid. The salt in powder form according to claim 8, wherein the liquid hydrocarbon is selected from the group consisting of oils, mineral spirits and non-aromatic hydrocarbons. The salt in powder form according to claim 1, which contains about 8% to about 70% by weight of alkaline earth metal. The salt in powder form according to claim 10, wherein the alkaline earth metal is calcium contained in an amount of about 8% to about 30% by weight. An overbased amorphous calcium salt in the form of a powder of fatty acids consisting essentially of an isolated solid calcium carbonate complex complexed with an amorphous calcium carboxylate of a fatty acid and an amorphous calcium carbonate complex salt. 13. The salt of claim 12 in powder form dispersible in a liquid hydrocarbon. 13. The salt of claim 12, wherein the micelle is on the order of about 50 microns. The salt of claim 13, wherein the liquid hydrocarbon is an oil. 14. Salt in powder form according to claim 13, wherein the liquid hydrocarbon is selected from the group consisting of oils, spirits and non-aromatic hydrocarbons. 13. The salt in powder form according to claim 12, wherein the fatty acid is a C ₁₂ -C ₂₂ fatty acid. 13. The salt in powder form according to claim 12, wherein the fatty acid is oleic acid. 13. A salt in powder form according to claim 12 containing from about 8% to about 70% by weight calcium. The salt of claim 12, wherein the calcium is contained in an amount of at least about 15% to about 30% by weight. Reacting the alkaline earth metal base and the fatty acid in the presence of a liquid hydrocarbon with an alkaline earth metal salt group to the fatty acid in an equivalent ratio of at least 1: 1; Acidifying the mixture to prepare an amorphous alkaline earth metal salt from the group consisting of carbonates, sulfates, sulfides and sulfites complexed with amorphous alkaline earth metal carboxylates of fatty acids in the liquid hydrocarbons; Precipitating from liquid hydrocarbon solid particles of an amorphous alkaline earth metal salt selected from the group consisting of carbonates, sulfates, sulfides and sulfites complexed with amorphous alkaline earth metal carboxylates of fatty acids; And Separating the solid particles in the form of an overbased amorphous alkaline earth metal salt in powder form, to prepare an overbased amorphous alkaline earth metal salt in powder form of a fatty acid. The method of claim 21, comprising separating the particles by filtration. The method of claim 21, wherein the precipitation step is performed by adding a solvent for the liquid hydrocarbon. The method of claim 21, wherein the fatty acid is a C ₁₂ -C ₂₂ fatty acid. The method of claim 21, wherein the fatty acid is oleic acid. The method of claim 22, wherein the particles are dried. The method of claim 21 wherein the alkaline earth metal is selected from the group consisting of calcium, barium, magnesium and strontium. 22. The method of claim 21 wherein the alkaline earth metal is calcium and the mixture is acidified by carbonization to form amorphous calcium carbonate complexed with amorphous alkaline earth metal carboxylate. The method of claim 28, wherein the overbased salt in powder form is calcium oleate / carbonate. The method of claim 23, wherein the solvent is an alcohol. The method of claim 21, wherein the reaction is carried out in the presence of an alcohol promoter. 32. The method of claim 31 wherein the alcohol has 8 to 14 carbon atoms. 32. The method of claim 31, further comprising glycol or glycol ether. The method of claim 33, wherein the glycol or glycol ether is selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof. The method chosen. 22. The method of claim 21 wherein based on the final reaction mixture, about 15 to 30% calcium hydroxide, about 12 to 24% magnesium hydroxide, about 25 to 50% strontium hydroxide, about 35 to 50% barium hydroxide, and mixtures thereof Reacting the amount of alkaline earth metal base selected from the group consisting of: 36. The method of claim 35, wherein the alkaline earth metal base is calcium hydroxide and the fatty acid is oleic acid. Reacting calcium hydroxide base and oleic acid in an equivalent ratio of at least 1: 1 base to acid in the presence of a mixture of liquid hydrocarbon and catalyst; Carbonizing the mixture to produce amorphous calcium carbonate; During the carbonization, adding calcium hydroxide, liquid hydrocarbons, and cosurfactant aliphatic alcohols having 8 or more carbon atoms in relative amounts at a controlled rate of calcium hydroxide addition to produce a liquid reaction product; Removing water from the reaction product to provide an overbased amorphous calcium oleate / carbonate in the liquid hydrocarbon; Precipitating from liquid hydrocarbon solid particles of amorphous calcium carbonate complexed with amorphous alkaline earth metal carboxylates of fatty acids; And Separating the solid particles in the form of an overbased amorphous alkaline earth metal salt in the form of a powder, the method of producing an overbased amorphous calcium oleate / carbonate in powder form. 38. The process of claim 37, wherein the catalyst is selected from the group consisting of propionic acid, citric acid, acetic acid and adipic acid. 38. The method of claim 37, wherein the cosurfactant is an aliphatic alcohol having 8 to 14 carbon atoms. 40. The method of claim 39, wherein the selected alcohol is isodecanol in the presence of diethylene glycol monobutyl ether and triethylene glycol. 38. The method of claim 37, wherein after addition of the dispersion and carbonization with carbon dioxide, the mixture comprises about 15 to 30% calcium oleate, about 9 to 35% calcium carbonate, about 30 to 35% hydrocarbon oil, about 15 to 18% isodeca Knol and methods containing about 4 to 6% glycol or glycol ether. 42. The method of claim 41 wherein the dispersion contains about 40-50% calcium hydroxide, about 25-40% hydrocarbon oil, about 10-25% isodecanol and about 0-10% glycol or glycol ether. 38. The method of claim 37, wherein the solvent for the liquid hydrocarbon is added to precipitate the solid particles. The method of claim 43, wherein the solvent is an alcohol selected from the group of isopropyl alcohol, methanol, ethanol, propanol, butanol, and glycol ethers. The method of claim 43, wherein the particles are separated by filtration and drying. The method of claim 37, wherein the particles are on the order of about 50 microns.